CN1769313A - Olefin/polar alpha-olefin copolymer and preparation method and uses - Google Patents
Olefin/polar alpha-olefin copolymer and preparation method and uses Download PDFInfo
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- CN1769313A CN1769313A CN 200410088511 CN200410088511A CN1769313A CN 1769313 A CN1769313 A CN 1769313A CN 200410088511 CN200410088511 CN 200410088511 CN 200410088511 A CN200410088511 A CN 200410088511A CN 1769313 A CN1769313 A CN 1769313A
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Abstract
The invention provides the alkene polymerization catalyst which possesses high polymerization activity and the method of preparing alkene polar monomer copolymer by using the said catalyst. The catalyst comprises (A) and (B). The (A) comprises transition metal compound whose general formula is (I), and the (B) comprises the metal organic compound or organic aluminoxane compound or ionized ionic compound. In the transition metal compound of general formula (I), the M is at the IIIB or IVB in the periodic table of elements, m is a integer between 1 and 3, R1 is alkene, R2 - R5 are H, halogen, hydrocarbon radical and so on, R6 is halogen or hydrocarbon radical and so on, and X is halogen or hydrocarbon radical and so on. The alkene used in combined polymerization comprises the all alkene which can coordinate and polymerize, the polar monomer comprises the alpha-alkene polar monomer which can coordinate and polymerize and includes N, O, P, S, B, Si, halogen and so on.
Description
Technical field
The present invention relates to a kind of alkene/polarity alpha-olefin copolymer, particularly, the present invention relates to a kind of alkene that contains various polar groups, has specified molecular weight and composition/polarity alpha-olefin copolymer.
The invention still further relates to a kind of preparation method of above-mentioned multipolymer.
The invention still further relates to the application of above-mentioned multipolymer.
Background technology
The copolymerization of alkene and other alpha-olefin, non-conjugated diene hydrocarbon, cycloolefin and esters of acrylic acid polar monomer is to improve one of effective ways of polyolefine physics and chemical property.The adding of comonomer can provide reactive group, improves polyolefinic physical and mechanical property simultaneously.On the other hand, in polyreaction, introduce functional groups, polyolefin products is carried out simple, effective and practicable functional modification, can improve polyolefinic surface polarity greatly, improve polyolefinic printing and dyeing and with the consistency of other material (as polar polymer, pigment, filler, glass fibre and metal etc.), with application extension to a brand-new field of polyolefin products.
About the copolymerization of alkene and polar monomer and since the exposed metal active center of traditional Ziegler-Natta catalyst very easily with atom combinations such as the oxygen that contains lone-pair electron of polar monomer, nitrogen, cause poisoning of catalyst and can not carry out polymerization.The nineties in last century, the copolymerization of carrying out alkene and polar monomer with metallocene catalyst grows up gradually, and common way is first with MAO or TMA pre-treatment polar monomer, heteroatomss such as oxygen, nitrogen is protected carry out copolymerization again.Generally speaking, metallocene is bridge metallocenes sterically hindered big more particularly, and the substituting group that contains around the polar monomer heteroatoms is big more, helps the generation of copolyreaction more.The mid-90 scientist finds, the late transition metal catalyst of weak oxytropism can carry out the copolymerization of alpha-olefin such as ethene and polar monomer, prepares the functional polyolefin material.Brookhart etc. report the multipolymer that obtains high-molecular weight acrylate and ethene or propylene by polycoordination first, but the copolymerization activity is lower.Chien
]The copolymerization activity of alpha-diimine Ni (II) title complex of report is higher, and the comonomer that is adopted is respectively acrylamide (AA), ε-Ji Neixianan (LA) and tetrahydrofuran (THF) (THF).Grubbs etc. have reported salicylic alidehyde imine Ni catalyzer in the presence of ester, ether, ketone, alcohol, amine and water isopolarity material, and the polymerization activity of catalyzer is unaffected substantially.Though they are insensitive to polar group, still there are two problems at present: the first, chain transfer reaction takes place when being used for olefinic polymerization easily cause molecular weight on the low side; The second, can not prepare the high functional polyolefin of tacticity.Therefore, solve the focus that these two problems have just become research,, just can transform, obtain huge achievement to industrial production in case break through.
How to improve the consistency of polyolefine and other material and bounding force and be always researcher one of the research direction of effort for it.The present invention is directed to different application targets, the new catalyst that composite structure is different is selected different reactive comonomer, seeks best polymeric reaction condition, and structure is special in the hope of obtaining, the polyolefin copolymer of excellent performance and functional polyolefin.A polyolefine printing and dyeing property and a difficult problem bad with other material compatibility that this just might solve long-term puzzlement people have new achievement in theory in polycoordination.Application prospect is also very wide.
Summary of the invention
One of purpose of the present invention provides a kind of alkene/polarity alpha-olefin copolymer, and the structure that it had can have the multiple functional group of height ratio and can be used as the raw material of multiple expanding material.
Another object of the present invention provides the method for the above-mentioned multipolymer of preparation.
For achieving the above object, alkene provided by the invention/polarity alpha-olefin copolymer composition copolymer is characterized in that:
(1) comprises the polarity alpha-olefin that contains 3-11 carbon atom of the olefin unit and 0.1～70% (mole) of 30～99.9% (moles);
(2) number-average molecular weight (M that records by gel chromatography (GPC)
n) be 500-300,000, molecular weight distribution (M
w/ M
n) scope is between 1.0～5.0;
(3) all polymer chains have at least 95% to have at least one unsaturated link(age) in its molecular end;
(4) the B value that is provided by following formula (I) is 1.0-2.0:
B＝P
PO/(2P
P·P
O) (I)
In the formula, P
OBe the molfraction of olefin unit in the multipolymer, P
PBe the unitary molfraction of multipolymer Semi-polarity alpha-olefin, P
POBe that polarity alpha-olefin/alkene sequence number accounts for the ratio of all binary sequence numbers.
The above-mentioned multipolymer of preparation provided by the invention can make by using a kind of olefin polymerization catalysis copolymerization alkene and the polarity alpha-olefin that contains 3-11 carbon atom, and described olefin polymerization catalysis comprises:
(A) transistion metal compound of representing with following formula (II),
(B) at least aly be selected from following compound:
(B-1) organometallic compound,
(B-2) the Organoaluminoxy hydride compounds and
(B-3) can with the right compound of transistion metal compound (A) reacting forming ion:
M is the transition metal atoms in the periodic table of elements 3-11 family in the formula,
M is the integer of 1-6,
R
1-R
6Can be identical or different; and be respectively hydrogen atom; halogen atom; alkyl; the heterogeneous ring compound residue; contain the oxygen base; nitrogenous base; contain boryl; contain sulfenyl; phosphorous-containigroups groups; contain silica-based; germanic base; contain tinbase; the silyl that hydrocarbon replaces; the siloxy-that hydrocarbon replaces; alkoxyl group; alkylthio; aryloxy; arylthio; acyl group; ester group; thioester substrate; amido; acylimino; amino; imino-; the sulphur ester group; sulfonamido; cyano group or nitro; and two or more groups can be incorporated into ring in them
N is a number that satisfies the M valence state,
X is hydrogen atom, halogen atom, alkyl, contain the oxygen base, contain sulfenyl, contain boryl, contain aluminium base, phosphorous-containigroups groups, contain halogen, heterogeneous ring compound residue, contain silica-based, germanic base or contain tinbase, when n is 2 or when bigger, a plurality of X groups can be identical or different, and can be incorporated into ring.
Alkene of the present invention/polarity alpha-olefin copolymer can be used as the superpolymer expanding material, contains multiple functional group, and the kind of functional group is controlled with its composition in multipolymer.
Alkene of the present invention/polarity alpha-olefin copolymer can be used as the reactive polymer blended material, directly forms interfacial compatibilizer in polyolefine and other material carry out the process of blend, improves the consistency of polyolefine and other material.
Embodiment
Below illustrate in greater detail the alkene that the present invention relates to and the preparation method of polarity alpha-olefin copolymer.
Alkene/polarity alpha-olefin copolymer
Alkene of the present invention/polarity alpha-olefin copolymer comprises alkene and contains the polarity alpha-olefin of 3-11 carbon atom.The example that is used for the polarity alpha-olefin of the 3-11 of containing an of the present invention carbon atom comprises that containing one or more polar groups is in two keys carbon atom in addition, polar group comprises halogen atom, alkyl, contains the oxygen base, nitrogenous base, contain boryl, contain sulfenyl, phosphorous-containigroups groups, contain silica-based group, and two or more groups can be incorporated into ring in them.Wherein good especially is the 1-hexene and the 1-hendecene of terminal hydroxyl, carboxyl, ester group, carbonyl, amino, amido.The example that is used for alkene of the present invention comprises ethene, propylene, contains the alpha-olefin of 3-10 carbon, conjugated diene, non-conjugated diene hydrocarbon.Wherein good especially is ethene, propylene, contain the alpha-olefin of 3-10 carbon.
Alkene of the present invention/polarity alpha-olefin copolymer comprises the polarity alpha-olefin unit of the olefin unit of 30-99.9% (mole) and 0.1-70% (mole) as the component unit.
Number-average molecular weight (the M of alkene of the present invention/polarity alpha-olefin copolymer
n) and molecular weight distribution (M
w/ M
n) can measure as standard specimen with monodisperse polystyrene with gel chromatography (GPC).Number-average molecular weight (the M of the alkene that records in this method/polarity alpha-olefin copolymer
n) at 500-300, in 000 the scope.In addition, the molecular weight distribution of alkene/polarity alpha-olefin copolymer is between 1.0-5.0, and is reasonable 3.0 or littler.
In alkene of the present invention/polarity alpha-olefin copolymer, in side chain, have various polar groups, polar group is at the position of side chain and the content in multipolymer and distribute and can control by the condition of telocopolymerization.
In alkene of the present invention/polarity alpha-olefin copolymer, the polarity alpha-olefin inserts with the position irregularity, therefore exists
13Observe the concrete signal of α β carbon in the C-NMR spectrogram, its is as based on the concrete signal of methene chain between adjacent two tertiary carbon atoms in the copolymer chain.
In addition, the B value by following formula (I) expression of alkene of the present invention/polarity alpha-olefin copolymer is 1.0-2.0:
B＝P
PO/(2P
P·P
O) (I)
In the formula, P
OBe the molfraction of olefin unit in the multipolymer, P
PBe the unitary molfraction of multipolymer Semi-polarity alpha-olefin, P
POBe that polarity alpha-olefin/alkene sequence number accounts for the ratio of all binary sequence numbers.
Along with the B value becomes big, the number of block class sequence diminishes, and means being evenly distributed of alkene and polarity alpha-olefin, the composition narrowly distributing of multipolymer.
Preparation alkene/polarity alpha-olefin copolymer
Alkene of the present invention/polarity alpha-olefin copolymer can by be used for olefin polymerization catalysis in the presence of copolymerization alkene and the polarity alpha-olefin that contains 3-11 carbon atom make, described catalyzer comprises:
(A) transistion metal compound of representing with following formula (II),
(B) at least aly be selected from following compound:
(B-1) organometallic compound,
(B-2) the Organoaluminoxy hydride compounds and
(B-3) can with the right compound of transistion metal compound (A) reacting forming ion:
(dotted line in the formula among the N----M (----) ordinary representation coordination, however it does not always represent coordination in the present invention.)
In general formula (II), M is 3-11 family in the periodictable (the 3rd family comprises group of the lanthanides), be preferably 3-9 family (the 3rd family comprises group of the lanthanides), more preferably 3-5 and 9 families, and good especially is the transition metal atoms of the 4th and the 5th family.The example of these atoms metals comprises scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, cobalt, rhodium, yttrium, chromium, molybdenum, tungsten, manganese, rhenium, iron and ruthenium.Wherein preferably scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, cobalt and rhodium; More preferably titanium, zirconium, hafnium, cobalt, rhodium, vanadium, niobium and tantalum; Particularly preferably be titanium, zirconium and hafnium.
M is the integer of 1-6, is preferably an integer among the 1-4.
R
1-R
6Can be identical or different; and be respectively hydrogen atom, halogen atom, alkyl, heterogeneous ring compound residue, contain oxygen base, nitrogenous base, contain boryl, contain sulfenyl, phosphorous-containigroups groups, contain silica-based, germanic base, contain tinbase, the silyl that hydrocarbon replaces, siloxy-, alkoxyl group, alkylthio, aryloxy, arylthio, acyl group, ester group, thioester substrate, amido, acylimino, amino, imino-, sulphur ester group, sulfonamido, cyano group or the nitro that hydrocarbon replaces, and two or more groups can be incorporated into ring in them.
Halogen atom is fluorine, chlorine, bromine and iodine.
The example of alkyl comprises 1-30 carbon atom, is preferably the straight or branched alkyl of 1-20 carbon atom, as methyl, ethyl, n-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, neo-pentyl and n-hexyl;
Contain 2-30, be preferably the straight or branched thiazolinyl of 2-20 carbon atom, as vinyl, allyl group and pseudoallyl;
Contain 2-30, be preferably the straight or branched thiazolinyl of 2-20 carbon atom, as vinyl, allyl group and pseudoallyl;
Contain 2-30, be preferably the straight or branched alkynyl of 2-20 carbon atom, as ethynyl and propargyl;
Contain 3-30, be preferably the cyclic saturated hydrocarbon base of 3-20 carbon atom, as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl;
The ring-type unsaturated alkyl that contains 5-30 carbon atom is as cyclopentadienyl, indenyl and fluorenyl; With
Contain 6-30, be preferably the aryl of 6-20 carbon atom, as phenyl, benzyl, naphthyl, xenyl, terphenyl, phenanthryl and anthryl; With
The aryl that alkyl replaces is as tolyl, cumyl, trimethylphenylmethane base, xylyl and two trimethylphenylmethane bases.
In above-mentioned alkyl, hydrogen atom can be replaced by halogen atom, and these contain 1-30, and the example that is preferably the halo alkyl of 1-20 carbon atom comprises trifluoromethyl, pentafluorophenyl group and chloro-phenyl-(cholophenyl).
Above-mentioned alkyl also can be replaced by other alkyl, and the example of the alkyl that these aryl replace comprises benzyl or cumyl.
In addition, above-mentioned alkyl also can have the heterogeneous ring compound residue; Contain the oxygen base, close base (carbonato), alkyl, peroxy and acid anhydride as alkoxyl group, aryloxy, ester group, ether, acyl group, carboxyl carbon acid group; Nitrogenous base is as amino, imino-, amido, acylimino, diazanyl, hydrazono-, nitro, nitroso-group, cyano group, isocyano-, cyanato, amidino groups, diazo and the ammonium salt that obtained by amino; Contain boryl, as methylene boryl (borandiyl), inferior first boryl (borantriyl) and diborane base; Contain sulfenyl, as sulfydryl, thioester substrate, dithioesters base, alkylthio, arylthio, sulfo-acyl group, thioether group, thiocyano, isocyanide sulfenyl, sulfonate group (sulfonato ester group), the ethylsulfonic acid root closes base and the phenylbenzimidazole sulfonic acid root closes base; The preferred example of sulfonamido comprises phenyl sulfonamido, N-sulfonyloxy methyl amino and N-methyl tolysulfonyl amino.
R
6Be preferably hydrogen substituting group in addition.Be R
6Better be halogen atom, alkyl, heterogeneous ring compound residue, contain the oxygen base, contain boryl, contain sulfenyl, contain silica-based, germanic base or contain tinbase.R
6Be preferably the silyl of halogen atom, alkyl, heterogeneous ring compound residue, hydrocarbon replacement, siloxy-, alkoxyl group, alkylthio, aryloxy, arylthio, acyl group, ester group, sulfo-ester group, amido, acylimino, amino, imino-, sulfonate group, sulfonamido, cyano group or the nitro that hydrocarbon replaces especially, be more preferably the silyl that halogen atom, alkyl or hydrocarbon replace.
As R
6Preferred alkyl example comprise and contain 1-30, be preferably the straight or branched alkyl of 1-20 carbon atom, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, neo-pentyl or n-hexyl; Contain 3-30, be preferably the cyclic saturated hydrocarbon base of 3-20 carbon atom, as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or adamantyl; Contain 6-30, be preferably the aryl of 6-20 carbon atom, as phenyl, benzyl, naphthyl, xenyl or terphenyl.Above-mentioned substituted group can be substituted base and further replace, these substituting groups are as containing 1-30, better contain 1-20 carbon atom alkyl or alkoxyl group, contain 1-30, better contain 1-20 carbon atom alkyl or alkoxyl group, contain 1-30, better contain 1-20 carbon atom haloalkyl, contain 6-30, better contain aryl or aryloxy, halogen, cyano group, nitro or the alkyl of 6-20 carbon atom.
As R
6The preferred example of the silyl that replaces of hydrocarbon comprise methyl-silicane base, dimetylsilyl, trimethyl silyl, ethyl silicane base, diethylsilane base, triethylsilyl, diphenyl methyl silyl, triphenyl silyl, 3,5-dimethylphenyl silyl, dimethyl tertiary butyl silyl, dimethyl pentafluorophenyl group silyl.Particularly preferably be trimethyl silyl, triethyl phenyl, diphenyl methyl silyl, isophenylsilyl, 3,5-dimethylphenyl silyl, dimethyl tertiary butyl silyl and dimethyl (pentafluorophenyl group) silyl.
In the present invention, R
6Preferred example be to be selected from:
Contain 3-30, better contain the branched-chain alkyl of 3-20 carbon atom, as sec.-propyl, isobutyl-, sec-butyl, the tertiary butyl and neo-pentyl;
The hydrogen atom of above-mentioned branched-chain alkyl is contained 6-30, better contains the group of the aryl replacement of 6-20 carbon atom, as cumyl;
Contain 3-30, better contain the cyclic saturated hydrocarbon base of 3-20 carbon atom, as adamantyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;
Contain 6-30, better contain the aryl of 6-20 carbon atom, as phenyl, naphthyl, fluorenyl, anthryl and phenanthryl; With
The silyl that hydrocarbon replaces.
Two or more R
1-R
6The hydrocarbon ring that group (preferably adjacent group) can interosculate and form alicyclic ring, aromatic ring or contain heteroatoms (as nitrogen-atoms), and these rings all can also contain substituting group.
When m is 2 or when bigger, R
1-R
6In the group two can how much.In addition, when m is 2 or when bigger, a plurality of R
1, R
2, R
3, R
4, R
5Or R
6Can be identical or different.
N is a number that satisfies the M valence state, as 0-5, better is 1-4, is more preferably 1-3,
X is hydrogen atom, halogen atom, alkyl, contain the oxygen base, contain boryl, contain aluminium base, phosphorous-containigroups groups, contain halogen, heterogeneous ring compound residue, contain silica-based, germanic base or contain tinbase, when n is 2 or when bigger, a plurality of X groups can be identical or different.
Halogen atom comprises fluorine, chlorine, bromine and iodine.
The example of alkyl comprises with above R
1-R
6Identical group in the description.Particularly, can exemplify, when being not limited to:
Alkyl is as methyl, ethyl, propyl group, butyl, hexyl, octyl group, nonyl, dodecyl and eicosyl;
The cycloalkyl that contains 3-30 carbon atom is as cyclopentyl, cyclohexyl, norborneol alkyl and adamantyl;
Thiazolinyl is as vinyl, propenyl and cyclohexenyl;
Aralkyl is as benzyl, styroyl and hydrocinnamyl; With
Aryl is as phenyl, tolyl, xylyl, trimethylphenyl, ethylbenzene base, propyl phenyl, xenyl, naphthyl, methyl naphthyl, anthryl and phenanthryl.These alkyl can also comprise the halo alkyl, more specifically comprise the group that has at least a hydrogen atom to be replaced by halogen atom in the alkyl of 1-30 carbon atom.
The alkyl that wherein preferably contains 1-20 carbon atom.
The example of heterogeneous ring compound residue comprises with above R
1-R
6Identical group in the description.
The example that contains the oxygen base comprises with above R
1-R
6Identical group in the description.Can exemplify particularly but be not limited to: alkyl; Alkoxyl group is as methoxyl group, oxyethyl group, propoxy-and butoxy; Aryloxy is as phenoxy group, methylphenoxy, dimethyl phenoxy and naphthyloxy; And aralkoxy, as phenyl methoxyl group and phenyl ethoxy; Acetoxyl group; And carbonyl.
The example that contains sulfenyl comprises with above R
1-R
6Identical group in the description.Can exemplify particularly but be not limited to: sulfonate radical closes base (sulfonato group), closes base, trifluoromethayl sulfonic acid root as the methylsulphonic acid root and closes base, Isobuytel Benzene sulfonate radical and close base, p-chlorobenzenesulfonic acid root and close base, tosic acid root and close base, trimethylbenzene sulfonate radical and close that base, three Isobuytel Benzene sulfonate radicals close base, the p-chlorobenzenesulfonic acid root closes base and the penta fluoro benzene sulfonate radical closes base; The-sulfinic acid root closes base, as methyl-sulfinic acid root close base, phenyl-sulfinic acid root close base, benzyl-sulfinic acid root close base, to the toluenesulfinic acid root close base, trimethylbenzene-sulfinic acid root closes base and penta fluoro benzene-sulfinic acid root closes base; Alkylthio and arylthio.
The example of nitrogenous base comprises with above R
1-R
6Identical group in the description.Can exemplify particularly but be not limited to: amino; Alkylamino is as methylamino-, dimethylamino, diethylin, dipropyl amino, dibutylamino and dicyclohexyl amino; Virtue amino and alkyl aryl amino are as phenylamino, diphenylamino, dimethylbenzene amino, two naphthylaminos and aminomethyl phenyl amino.
The example that contains boryl comprises BR
4(R is hydrogen, alkyl, can has substituent aryl, halogen atom etc.).
The example of phosphorous-containigroups groups includes but not limited to: the trialkyl phosphino-, as trimethyl-phosphine, tributylphosphine and tricyclohexyl phosphine; The triaryl phosphino-is as triphenylphosphine and trimethylphenyl phosphine; Phosphorous acid base (phosphidogroup) is as methyl phosphorous acid base, ethyl phosphorous acid base and phenyl phosphorous acid base; Phosphonate group; With the phospho acid base.
Containing silica-based example comprises with above R
1-R
6Identical group in the description.Can exemplify particularly but be not limited to: the silyl that hydrocarbon replaces, as phenyl silyl, diphenylmethyl silylation, trimethyl silyl, triethylsilyl, tripropyl silyl, thricyclohexyl silyl, triphenyl silyl, methyldiphenyl base silyl, trimethylphenyl silyl and three naphthyl silyls; The silyl ether that hydrocarbon replaces is as the trimethyl silyl ether; The alkyl that silicon replaces is as the trimethyl silyl methyl; The aryl that silicon replaces is as the trimethyl silyl phenyl.
The example of germanic base comprises with above R
1-R
6Identical group in the description.Can exemplify the group that above-mentioned silicon in silica-based is replaced by germanium particularly.
The example that contains tinbase comprises with above R
1-R
6Identical group in the description.Can exemplify the group that the above-mentioned silicon that contains in silica-based is replaced by tin particularly.
The example that contains halogen comprise contain fluorine-based, as PF
6And BF
4Contain chloro, as ClO
4And SbCl
6With contain iodo, as IO
4, but be not limited thereto.
Contain aluminium base example and comprise AlR4 (R is hydrogen, alkyl, can has substituent aryl, halogen atom etc.), but be not limited thereto.
But n is 2 or when bigger, and a plurality of groups of being represented by X can be identical or different, and a plurality of group of representing by X can be incorporated into ring,
(B-1) organometallic compound
The example that is used for organometallic compound of the present invention (B-1) comprises the organometallic compound that contains periodictable 1 family, 2 families, 12 families and 13 family's metals, as following compound.
(B-1a) organo-aluminium compound that is expressed from the next:
R
a mAl(OR
b)
nH
pX
q
In the formula, Ra and Rb can be identical or different, show the alkyl of 1-15 carbon atom separately, are preferably the alkyl of 1-4 carbon atom; X is a halogen atom; M, n, p and q are the numbers of 0≤m＜3,0≤n＜3,0≤p＜3,0≤q＜3 and m+n+p+q=3 of satisfying condition.
(B-1b) alkyl complexes that contains periodictable 1 family's metal and aluminium that is expressed from the next:
M
2AlR
a 4
In the formula, M
2Be Li, Na or K; R
aBe 1-15, better be the alkyl of 1-4 carbon atom.
(B-1c) dialkyl compound that contains periodictable 2 family's metals or 12 family's metals that is expressed from the next:
R
aR
bM
3
In the formula, R
aAnd R
bCan be identical or different, each naturally 1-15, better be the alkyl of 1-4 carbon atom; M
3Be Mg, Zn or Cd.
The example of organo-aluminium compound (B-1a) comprising:
The organo-aluminium compound that is expressed from the next:
R
aAl(OR
b)
3-m
In the formula, R
aAnd R
bCan be identical or different, each naturally 1-15, better be the alkyl of 1-4 carbon atom; M better is the number of 1.5≤m＜3 of satisfying condition;
The organo-aluminium compound that is expressed from the next:
R
a mAlX
3-m
In the formula, Ra is 1-15 carbon atom, better is the alkyl of 1-4 carbon atom; X is a halogen atom; M better is the number of 0＜m＜3 of satisfying condition;
The organo-aluminium compound that is expressed from the next:
R
a mAlH
3-m
In the formula, R
aFor 1-15, better be the alkyl of 1-4 carbon atom; M better is the number of 2≤m＜3 of satisfying condition; With
The organo-aluminium compound that is expressed from the next:
R
a mAl(OR
b)
nXq
In the formula, Ra and Rb can be identical or different, each naturally 1-15, better be the alkyl of 1-4 carbon atom; X is a halogen atom; M, n and q are the numbers of 0≤m＜3,0≤n＜3,0≤q＜3 and m+n+q=3 of satisfying condition.
The object lesson of organo-aluminium compound (B-1a) comprising:
Three positive aluminum alkylss are as trimethyl aluminium, triethyl aluminum, three n-butylaluminum, tri-propyl aluminum, three amyl group aluminium, three hexyl aluminium, trioctylaluminum and three decyl aluminium;
The side chain trialkylaluminium is as triisopropylaluminiuand, triisobutyl aluminium, three sec-butyl aluminium, tri-tert aluminium, three-2-methyl butyl aluminium, three-3-methyl butyl aluminium, three-2-methyl amyl aluminium, three-3-methyl amyl aluminium, three-4-methyl amyl aluminium, three-2-methyl hexyl aluminium, three-3-methyl hexyl aluminium and three-2-ethylhexyl aluminium;
Tricyclic alkyl aluminium is as thricyclohexyl aluminium and three ring octyl group aluminium;
Triaryl aluminum is as triphenyl aluminum and trimethylphenyl aluminium;
The hydrogenation aluminum dialkyl is as diisobutylaluminium hydride;
Trialkenyl aluminium is as by formula (i-C
4H
9)
xAly (C
5H
10)
z(wherein each positive number naturally of x, y and z, and z 〉=2x) the trialkenyl aluminium of expression, for example three prenyl aluminium (triisoprenylaluminum);
Alkoxyalkyl aluminium is as methoxyl group aluminium isobutyl, oxyethyl group aluminium isobutyl and isopropoxy aluminium isobutyl;
The alkoxyl group aluminum dialkyl is as methoxyl group dimethyl aluminium, oxyethyl group diethyl aluminum and fourth chloro dibutyl aluminium;
Sesquialter alkoxyalkyl aluminium, as sesquialter ethoxyethyl group aluminium and sesquialter butoxy butyl aluminium,
The aluminum alkyls of part alkoxide, as average composition by R
a 2.5Al (OR
b)
0.5The aluminum alkyls of the part alkoxide of expression;
The aryloxy aluminum dialkyl, as phenoxy group diethyl aluminum, (2,6-di-t-butyl-4-methylphenoxy) diethyl aluminum, two (2,6-di-t-butyl-4-methylphenoxy) aluminium triethyl, (2,6-di-t-butyl-4-methylphenoxy) diisobutyl aluminum and two (2,6-di-t-butyl-4-methylphenoxy) aluminium isobutyl;
Aluminum dialkyl monohalide, as chlorodimethylalumiu, diethylaluminum chloride, chlorination dibutyl aluminium, bromination diethyl aluminum and di-isobutyl aluminum chloride:
The sesquialter alkyl aluminum halide is as sesquialter ethylaluminium chloride, sesquialter chlorinated butyl aluminium and sesquialter bromination aluminium triethyl;
Partially halogenated aluminum alkyls, as the dihalo-aluminum alkyls, for example ethyl aluminum dichloride, two chloropropyl aluminium and two brombutyl aluminium;
The hydrogenation aluminum dialkyl, as diethyl aluminium hydride and hydrogenation dibutyl aluminium,
Partially hydrogenated aluminum alkyls, as the dihydro aluminum alkyls, for example dibydroethyl aluminium and dihydro propyl group aluminium; With
Part alkoxide and halogenated aluminum alkyls are as chlorination ethoxyethyl group aluminium, chlorination butoxy butyl aluminium and bromination ethoxyethyl group aluminium.
Also can use and organo-aluminium compound (B-1a) similar compounds.For example, the organo-aluminium compound that two or more aluminum compounds link together by nitrogen-atoms is as (C
2H
5)
2AlN (C
2H
5) Al (C
2H
5)
2
The example of compound (B-1b) comprises LiAl (C
2H
5)
4And LiAl (C
7H
15)
4
Other compound that also can be used as organometallic compound (B-1) comprises lithium methide, lithium ethide, propyl lithium, butyllithium, methylmagnesium-bromide, Repone K base magnesium, ethyl-magnesium-bromide, ethyl-magnesium-chloride, bromination propyl group magnesium, chlorination propyl group magnesium, butyl magnesium bromide, butyl magnesium chloride, dimethyl magnesium, magnesium ethide, dibutylmagnesium and butyl ethyl magnesium.
Also can use the mixture that can in polymerization system, make above-mentioned organo-aluminium compound, as the mixture of aluminum halide and lithium alkylide and the mixture of aluminum halide and alkyl magnesium.
In organometallic compound (B-1), be preferably organo-aluminium compound.
Above-mentioned organometallic compound (B-1) can use separately, and perhaps two or more are used in combination.
(B-2) Organoaluminoxy hydride compounds
Can choose that to be used for Organoaluminoxy hydride compounds of the present invention (B-2) can be the benzene-insoluble Organoaluminoxy compound that conventional aikyiaiurnirsoxan beta or Japanese publication communique No.78687/1990 are exemplified wantonly.
For example can make conventional aikyiaiurnirsoxan beta, and general what obtain is solution in hydrocarbon solvent by following method.
(1) organo-aluminium compound (as trialkylaluminium) is added contains the compound of planar water or contain in the hydrocarbon dielectric suspensions of salt (as hydrated magnesium chloride, hydrated copper sulfate, hydrazine aluminum sulfate, hydration nickel sulfate or hydration Cerium II Chloride) of crystal water, organo-aluminium compound and planar water or crystal water are reacted.
(2) in medium (as benzene, toluene, ether or tetrahydrofuran (THF)), water, ice or water vapor are directly acted on the organo-aluminium compound (as trialkylaluminium).
(3) in medium (as decane, benzene or toluene), make organotin oxides (as cacodyl oxide base tin or dibutyltin oxide) and organo-aluminium compound (as trialkylaluminium) reaction.
Described aikyiaiurnirsoxan beta contains a small amount of organo-metallic component.In addition, can be from the aluminoxanes solution that reclaims distillation remove and desolvate or unreacted organo-aluminium compound, and be dissolved in resistates in the solvent again or be suspended in the good Rong agent of aluminium chlorine alkane.
The example that is used for making the organo-aluminium compound of aikyiaiurnirsoxan beta comprises and the above identical organo-aluminium compound of description to organo-aluminium compound (B-1a).
Wherein, be preferably trialkylaluminium and tricyclic alkyl aluminium.Best is trimethyl aluminium.
Can use separately or two or more are used in combination organo-aluminium compound.
The example that is used to make the solvent of aikyiaiurnirsoxan beta comprises aromatic hydrocarbons, as benzene,toluene,xylene, isopropyl benzene and cymene; Aliphatic hydrocrbon is as pentane, hexane, heptane, octane, decane, dodecane, n-Hexadecane and octadecane; Alicyclic hydrocarbon is as pentamethylene, hexanaphthene, cyclooctane and methylcyclopentane; Petroleum fractions is as gasoline, kerosene and gas oil; And these aromatic hydrocarbons, aliphatic hydrocrbon and alicyclic halogenated products (as chlorizate and brominated product).Also can use ether, as ether and tetrahydrofuran (THF).In these solvents, good especially is aromatic hydrocarbons and aliphatic hydrocrbon.
Be used for benzene-insoluble Organoaluminoxy compound of the present invention and be preferably to be generally at 60 ℃ of Al group components that can be dissolved in benzene and be no more than 10%, better be no more than 5%, good especially 2% the Organoaluminoxy compound that is no more than in the Al atom.That is to say that ， Bu Rong is preferably in the Organoaluminoxy compound of benzene is insoluble to benzene or is slightly soluble in benzene.
The used Organoaluminoxy compound of the present invention for example is the Organoaluminoxy compound by the boracic of following formula (III) expression
R in the formula
17It is the alkyl of 1-10 carbon atom; Each R
18Can be identical or different, be the alkyl of hydrogen atom, a halogen atom or 1-10 carbon atom.
Can be under inert gas atmosphere react 1 minute to 24 hours with organo-aluminium compound and make by the Organoaluminoxy hydride compounds of the boracic of formula (III) expression in-80 ℃ of alkylboronic acidss that in inert solvent, make following formula (IV) expression to room temperature.
R
17-B-(OH)
2 (IV)
R in the formula
17Be and top described identical group.
Example by the alkylboronic acids of formula (IV) expression comprises methyl-boron-dihydroxide, ethyl-boron dihydroxide, sec.-propyl boric acid, n-propyl boric acid, normal-butyl boric acid, isobutyl-boric acid, n-hexyl boric acid, cyclohexyl boric acid, phenyl-boron dihydroxide, 3,5-difluoro boric acid (3,5-difluoroboronic acid), pentafluorophenyl group boric acid and 3,5-two (trifluoromethyl) phenyl-boron dihydroxide.Wherein, be preferably methyl-boron-dihydroxide, normal-butyl boric acid, isobutyl-boric acid, 3,5-difluorophenyl boric acid and pentafluorophenyl group boric acid.
These alkylboronic acidss can use separately or two or more are used in combination.
With the example of the organo-aluminium compound of alkylboronic acids reaction comprise with above organo-aluminium compound (B-1a) is described in identical organo-aluminium compound.
Wherein, be preferably trialkylaluminium and tricyclic alkyl aluminium.Good especially is trimethyl aluminium, triethyl aluminum and triisobutyl aluminium.These organic calorize platform things can use separately or two or more are used in combination.
Above-mentioned Organoaluminoxy hydride compounds (B-2) can use separately or two or more are used in combination.
(B-3) with the right compound of transistion metal compound reacting forming ion
The example that is used for the right compound (B-3) of of the present invention and transistion metal compound (A) reacting forming ion (below be referred to as " ionized ionic compound ") comprises Lewis acid, ionic compound, borane compound and carborane compound, as United States Patent (USP) 5, described in 321,106.Also can use heteropoly compound and with the polyvoltine compound.
Lewis acid is for example by BR
3The compound of (R is fluorine or the phenyl with substituting group (as fluorine, methyl or trifluoromethyl)) expression.The example of this compound comprises boron trifluoride, triphenyl-boron, three (4-fluorophenyl) boron, three (3, the 5-difluorophenyl) boron, three (4-methyl fluoride phenyl) boron, three (pentafluorophenyl group) boron, three (p-methylphenyl) boron, three (o-tolyl) boron and three (3, the 5-3,5-dimethylphenyl) boron.
Ionic compound is the compound of for example being represented by following formula V:
In following formula, R
19Be H
+, carbocation, oxygen positively charged ion, ammonium cation, phosphorus positively charged ion, cycloheptatriene base positively charged ion, have ferrocene (ferrocenium) positively charged ion of transition metal etc.
R
20-R
23Can be identical or different, each is organic group naturally, better is the aryl of aryl or replacement.
The example of carbocation comprises trisubstituted carbocation, as triphenylcarbenium positively charged ion, three (aminomethyl phenyl) carbocation and three (3,5-dimethylphenyl) carbocation.
The example of ammonium cation comprises the trialkyl ammonium positively charged ion, as trimethyl ammonium positively charged ion, triethyl ammonium positively charged ion, tripropyl ammonium cation, tributyl ammonium positively charged ion and three normal-butyl ammonium cations; N, N-dialkyl benzene ammonium cation, as N, N-dimethyl benzene ammonium cation, N, N-diethylbenzene ammonium cation and N, N-2,4,6-pentamethylbenzene ammonium cation: and the dialkyl ammonium positively charged ion, as di-isopropyl ammonium cation and dicyclohexyl ammonium cation.
The cationic example of phosphorus comprises triaryl phosphorus positively charged ion, as triphenyl phosphorus positively charged ion, three (aminomethyl phenyl) phosphorus positively charged ion and three (3,5-dimethylphenyl) phosphorus positively charged ion.
R
19Better be carbocation or ammonium cation, good especially is triphenylcarbenium positively charged ion, N, N-dimethyl benzene ammonium cation or N, N-diethylbenzene ammonium cation.
Also can be used as the ammonium salt, the N that have trialkyl to replace of ionic compound, N-dialkyl benzene ammonium salt, dialkyl ammonium salt and triaryl microcosmic salt.
The example of the ammonium salt that trialkyl replaces comprises: tetraphenyl boron triethyl ammonium, tetraphenyl boron tripropyl ammonium, tetraphenyl boron three normal-butyl ammoniums, four (p-methylphenyl) boron trimethyl ammonium, four (o-tolyl) boron trimethyl ammonium, four (pentafluorophenyl group) boron, three normal-butyl ammoniums, four (neighbours, right-xylyl) boron tripropyl ammonium, four (, between-xylyl) boron three normal-butyl ammoniums, four (p-trifluoromethyl phenyl) boron, three normal-butyl ammoniums, four (3,5-two or three cyanogen aminomethyl phenyls) boron three normal-butyl ammoniums and four (o-tolyl) boron, three normal-butyl ammoniums.
N, the example of N-dialkyl benzene ammonium salt comprises tetraphenyl boron N, N-dimethyl puratized agricultural spray, tetraphenyl boron N, N-diethyl puratized agricultural spray and tetraphenyl boron N, N-2,4,6-pentamethyl-puratized agricultural spray.
The example of dialkyl ammonium salt comprises four (pentafluorophenyl group) boron, two (1-propyl group) ammoniums and tetraphenyl boron dicyclohexyl ammonium.
What also can be used as ionic compound has four (pentafluorophenyl group) boric acid triphenylcarbenium, four (pentafluorophenyl group) boric acid N, N-dimethyl puratized agricultural spray, four (pentafluorophenyl group) boric acid ferrocene, pentapheneyl cyclopentadienyl triphenylcarbenium title complex, pentapheneyl cyclopentadienyl N, N-diethyl puratized agricultural spray title complex, and by the boron compound of following formula (VI) expression:
Wherein, Et is an ethyl, perhaps the boron compound of following formula (VII) expression:
The example of borane compound comprises:
Decaboron tetradecahydride (14);
Anion salt is as the ninth of the ten Heavenly Stems boric acid two (three normal-butyl ammoniums), the last of the ten Heavenly stems boric acid two (three normal-butyl ammoniums), 11-borate two (three normal-butyl ammoniums), ten hypoboric acid two (three normal-butyl ammoniums), ten chlorine boric acid in the last of the ten Heavenly stems two (three normal-butyl ammoniums) and ten dichloros, ten hypoboric acid two (three normal-butyl ammoniums); With
The metallo-borane anion salt is as two (ten dihydros, ten hypoboric acid) cobalt acid (III) three normal-butyl ammoniums and two (ten dihydros, ten hypoboric acid) nickel acid (III) two (tri-n-butyl amine).
The example of carborane compound comprises:
Anion salt, as 4-carbon for borine in the ninth of the ten Heavenly Stems (14), 1,3-two carbon are for borine in the ninth of the ten Heavenly Stems (13), 6,9-two carbon are for Decaboron tetradecahydride (14), ten dihydros-1-phenyl-1,3-two carbon are for borine in the ninth of the ten Heavenly Stems, ten dihydros-1-methyl isophthalic acid, 3-two carbon are for borine in the ninth of the ten Heavenly Stems, 11 hydrogen-1,3-dimethyl-1,3-two carbon are for borine in the ninth of the ten Heavenly Stems, 7,8-two carbon generation 11 borines (13), 2,7-two carbon generation 11 borines (13), 11 hydrogen-7,8-dimethyl-7,8-two carbon generation 11 borines, ten dihydros-11-methyl-2,7-two carbon generation 11 borines, 1-carbon is for boric acid three normal-butyl ammoniums in the last of the ten Heavenly stems, 1-carbon is for 11-borate three normal-butyl ammoniums, 1-carbon generation ten hypoboric acid, three normal-butyl ammoniums, 1-trimethyl silyl-1-carbon is for boric acid three normal-butyl ammoniums in the last of the ten Heavenly stems, bromo-1-carbon generation ten hypoboric acid, three normal-butyl ammoniums, 6-carbon is for boric acid (14) three normal-butyl ammoniums in the last of the ten Heavenly stems, 6-carbon is for boric acid (12) three normal-butyl ammoniums in the last of the ten Heavenly stems, 7-carbon is for 11-borate (13) three normal-butyl ammoniums, 7,8-two carbon are for 11-borate (12) three normal-butyl ammoniums, 2,9-two carbon boric acid (12) three normal-butyl ammoniums in 11 last of the ten Heavenly stems of generation, ten dihydros-8-methyl-7,9-two carbon are for 11-borate three normal-butyl ammoniums, 11 hydrogen-8-ethyl-7,9-two carbon are for 11-borate three normal-butyl ammoniums, 11 hydrogen-8-butyl-7,9-two carbon are for 11-borate three normal-butyl ammoniums, 11 hydrogen-8-allyl group-7,9-two carbon are for 11-borate three normal-butyl ammoniums, 11 hydrogen-9-trimethyl silyl-7,8-two carbon are for 11-borate three normal-butyl ammoniums and 11 hydrogen-4, and 6-two bromo-7-carbon are for 11-borate three normal-butyl ammoniums; And
The metallocarborane anion salt, as two (nine hydrogen-1,3-two carbon are for boric acid in the ninth of the ten Heavenly Stems) cobalt acid (III) three normal-butyl ammoniums, two (11 hydrogen-7,8-two carbon are for 11-borate) ferric acid (III) three normal-butyl ammoniums, two (11 hydrogen-7,8-two carbon are for 11-borate) cobalt acid (III) three normal-butyl ammoniums, two (11 hydrogen-7,8-two carbon are for 11-borate) nickel acid (III) three normal-butyl ammoniums, two (11 hydrogen-7,8-two carbon are for 11-borate) copper acid (III) three normal-butyl ammoniums, two (11 hydrogen-7,8-two carbon generation 11 boron saddles) auric acid (III) three normal-butyl ammoniums, two (nine hydrogen-7,8-dimethyl-7,8-two carbon are for 11-borate) ferric acid (III) three normal-butyl ammoniums, two (nine hydrogen-7,8-dimethyl-7,8-two carbon are for 11-borate) chromic acid (III) three normal-butyl ammoniums, two (tribromo eight oxygen-7,8-two carbon are for 11-borate) cobalt acid (III) three normal-butyl ammoniums, two (11 hydrogen-7-carbon is for 11-borate) chromic acid (III) three [(three normal-butyls) ammonium], two (11 hydrogen-7-carbon is for 11-borate) mangaic acid (IV) two [(three normal-butyls) ammonium], two (11 hydrogen-7-carbon is for 11-borate) cobalt acid (III) two [(three normal-butyls) ammonium and two (11 hydrogen-7-carbon is for 11-borate) nickel acid (IV) two [(three normal-butyls) ammonium.
Heteropoly compound comprises an atom in silicon, phosphorus, titanium, germanium, arsenic and the tin, and comprises the one or more atoms that are selected from vanadium, niobium, molybdenum and tungsten.The example of these compounds comprises the phosphorus vanadic acid, the germanium vanadic acid, the arsenic vanadic acid, the phosphorus niobic acid, the germanium niobic acid, silicomolybdic acid, phospho-molybdic acid, the titanium molybdic acid, the germanium molybdic acid, the arsenic molybdic acid, the tin molybdic acid, phospho-wolframic acid, germanotungstic acid, stannotungstic acid, molybdovanaphosphoric acid, tungstovanadophosphoric acid, germanium tungsten vanadic acid, P-Mo-Wo-V acid, Ge-Mo-Wo-V acid, P-Mo-Wo acid, P-Mo-Nb acid, the metal-salt that these are sour, specifically be that these acid and for example periodictable 1 family or 2 family's metals are (as lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium or barium) salt that become, and the organic salt of above-mentioned acid, as three styroyl salt, but be not limited to these compounds.
Above-mentioned ionized ionic compound (B-3) can use separately or two or more are used in combination.
In polymerization, can select any means to use and add component, use any order to add component, below provide some examples.
(1) with any order component (A) and at least a component (hereinafter referred is " component (B) ") that is selected from organometallic compound (B-1), Organoaluminoxy compound (B-2) and ionized ionic compound (B-3) are added in the polymerization reactor.
(2) with any order component (A) and component (B-1) being contacted the catalyst component and the component (B-3) that obtain in advance adds in the polymerization reactor.
(3) with any order component (A) and component (B-1) being contacted the catalyst component, component (B-1) and the component (B-3) that obtain in advance adds in the polymerization reactor.In this case, component (B-1) can be identical or different.
(4) with any order component (A) and component (B-1) and component (B-3) being contacted the catalyst component and the component (B-1) that obtain in advance adds in the polymerization reactor.In this case, component (B-1) can be identical or different.
(5) component (A) and component (B-2) being contacted in advance the catalyzer that obtains adds in the polymerization reactor.
(6) with any order component (A) and component (B-2) are contacted in the catalyst component and component (B-1) or component (B-2) adding polymerization reactor that obtains in advance.In this case, component (B-2) can be identical or different.
In the preparation method of alkene of the present invention/polarity alpha-olefin copolymer, the copolymerization in solution in the presence of above-mentioned olefin polymerization catalysis of alkene and polarity alpha-olefin obtains olefin copolymer.
In the present invention, can use any method (as solution polymerization or suspension polymerization) in the liquid polymerization to carry out polymerization.
The example that is used for the unreactive hydrocarbons medium of liquid polymerization comprises aliphatic hydrocrbon, as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; Alicyclic hydrocarbon is as pentamethylene, hexanaphthene and methylcyclopentane; Aromatic hydrocarbons is as benzene, toluene and dimethylbenzene; Halohydrocarbon is as ethylene chloride, chlorobenzene and methylene dichloride; And the mixture of these hydrocarbon.Alkene itself also can be used as solvent.
When using olefin polymerization catalysis to carry out olefinic polymerization, the consumption of component (A) is generally 10
-12-10
-2Mol is preferably 10
-10-10
-3Mol.
The consumption of component (B-1) is to make the mol ratio ((B-1)/(M)) of the transition metal atoms (M) in component (B-1) and the component (A) be generally 0.01-100,000, be preferably 0.05-50,000.
The consumption of component (B-2) is to make the aluminium atom in the component (B-2) and the mol ratio ((B-2)/(M)) of the transition metal atoms (M) in the component (A) be generally 10-500,000, be preferably 20-100,000.
The consumption of component (B-3) is to make the mol ratio ((B-3)/(M)) of the transition metal atoms (M) in component (B-3) and the component (A) be generally 1-10, is preferably 1.5.
When using olefin polymerization catalysis to carry out olefinic polymerization, polymerization temperature in-50 ℃ to 200 ℃ scope, is preferably 0-170 ℃ usually.Polymerization pressure usually at normal atmosphere to 100kg/cm
2Scope in, be preferably normal atmosphere to 50kg/cm
2Can use intermittently, any method in the semicontinuous and successive method carries out polyreaction.Can under different reaction conditionss, carry out polymerization by two steps or multistep.
Can regulate the molecular weight of gained alkene/polarity alpha-olefin copolymer by changing polymerization temperature.Molecular weight also can be regulated by the type that changes used component (B).In addition, molecular weight can also be regulated by hydrogen is present in the polymerization system.
The object lesson of preparation alkene/polarity alpha-olefin copolymer is as described below:
Embodiment 1: ethene/polarity alpha-olefin copolymer
Under nitrogen protection, to the dry deoxygenation of 250mL, be furnished with and add the 100mL dry toluene in the churned mechanically glass reactor, under agitation add 8.0mmol triisobutyl aluminium Al (
iBu)
3, (Al/Zr=770), feeding pressure is the ethylene gas of 76mmHg for MAO, the toluene solution of 1.4mol/L, and reactor is placed 25 ℃ water-bath, and polyreaction is adding 1.0 * 10 for 8.0mmol undecylenyl alcohol and 0.55mL methylaluminoxane
-6Begin behind the mol catalyzer (seeing structure shown in the following formula (VIII)).After the polymerization 5 minutes, add 5mL hcl acidifying ethanol and stop polyreaction, polymerisate filters the final vacuum drying until constant weight through washing with alcohol.Resulting polymers 1.6g,
1The HNMR test contains undecylenyl alcohol 0.67mol%.
Other is with embodiment 1, and the characteristic of operational condition and polyethylene/undecylenyl alcohol is listed in table 1.
Table 1 embodiment 1-10
a
| Embodiment | MAO/Ti mol/mol | Al(iBu) 3 Mmol | Undecylenyl alcohol mmol | Time mins | Catalytic efficiency b | Undecylenyl alcohol is content mol% in multipolymer |
| 1 2 3 4 5 6 7 | 770 770 770 770 420 1500 3000 | 8.0 5.6 4.0 1.6 4.0 4.0 4.0 | 8.0 5.6 4.0 1.6 4.0 4.0 4.0 | 5 5 5 5 5 5 5 | 1.92 1.78 1.99 2.58 2.32 2.11 1.49 | 0.67 0.51 0.40 0.21 0.54 0.61 0.68 |
aPolymerizing condition: temperature=25 ℃, ethylene pressure=0.1MPa, catalyst levels 2.0 μ mmol, 100mL toluene is solvent.
b10
-7gP(molTi
-1·h)
-1
Embodiment 8: propylene/polarity alpha-olefin copolymer
Other condition and embodiment 1 are identical, replace ethylene gas with propylene gas, replace undecylenyl alcohol with undecylenic acid, Al (iBu)
3With mol ratio=2 of undecylenic acid, resulting polymers Semi-polarity alpha-olefin content 0.10mol%.
Embodiment 9:1,5-hexadiene/polarity alpha-olefin copolymer
Under nitrogen protection, to the dry deoxygenation of 250mL, be furnished with and add the 90mL dry toluene in the churned mechanically glass reactor, under agitation add 8.0mmol triisobutyl aluminium Al (
iBu)
3, 8.0mmol undecylenyl alcohol and 0.55mL methylaluminoxane (MAO, the toluene solution of 1.4mol/L, Al/Zr=770), 10mL exsiccant 1,5-hexadiene monomer places 25 ℃ water-bath with reactor, polyreaction is adding 1.0 * 10
-6Begin behind the mol catalyzer.After the polymerization 24 hours, add 5mL hcl acidifying ethanol and stop polyreaction, polymerisate filters the final vacuum drying until constant weight through washing with alcohol.Resulting polymers 1.2g,
1The HNMR test contains polarity alpha-olefin 3.04mol%.
Embodiment 10:1-hexene/polarity alpha-olefin copolymer
Other condition and embodiment 9 are identical, replace 1 with the 1-hexene, 5-hexadiene, resulting polymers Semi-polarity alpha-olefin content 2.89mol%.
Embodiment 11: ethene/polarity alpha-olefin copolymer
Other condition is identical with embodiment 1, with B (C
6F
5)
3Replace MAO, B/Zr mol ratio=2, resulting polymers Semi-polarity alpha-olefin content 0.53mol%.
Embodiment 12: ethene/polarity alpha-olefin copolymer
Other condition is identical with embodiment 1, uses Ph
3C
+B (C
6F
5)
4 -Replace MAO, B/Zr mol ratio=2, resulting polymers Semi-polarity alpha-olefin content 0.45mol%.
Embodiment 13:1-octene and polarity alpha-olefin copolymer
Under nitrogen protection, to the dry deoxygenation of 250mL, be furnished with the dry 1-octene of adding 1mL in the churned mechanically glass reactor, under agitation add 8.0mmol trimethyl aluminium AlMe
3, (MAO, the toluene solution of 1.4mol/L Al/Zr=770), place 125 ℃ oil bath with reactor, and polyreaction is adding 1.0 * 10 for 8.0mmol hendecene ammonia and 0.55mL methylaluminoxane
-6Begin behind the mol catalyzer (structure shown in the formula IX as follows).After the polymerization 10 minutes, add 5mL hcl acidifying ethanol and stop polyreaction, polymerisate filters the final vacuum drying until constant weight through washing with alcohol.Resulting polymers 5.6g,
1The HNMR test contains hendecene ammonia 70mol%.
Embodiment 14: the multipolymer of vinylbenzene and polarity alpha-olefin
Under nitrogen protection, to the dry deoxygenation of 250mL, be furnished with adding 50mL dry benzene ethene in the churned mechanically glass reactor, under agitation add 1.0mmol triethyl aluminum AlEt
3, (MAO, the toluene solution of 1.4mol/L Al/Zr=770), place 0 ℃ ice-water bath with reactor, and polyreaction is adding 0.01 * 10 for 1.0mmol hendecene acid amides and 0.55mL methylaluminoxane
-6Begin behind the mol catalyzer (structure shown in the formula X as follows).After the polymerization 1 minute, add 20mL hcl acidifying ethanol and stop polyreaction, polymerisate filters the final vacuum drying until constant weight through washing with alcohol.Resulting polymers 0.6g,
1The HNMR test contains hendecene acid amides 0.1mol%.
Embodiment 15: the multipolymer of divinyl and polarity alpha-olefin
Under nitrogen protection, to the dry deoxygenation of 250mL, be furnished with the dry divinyl of adding 5.0mL in the churned mechanically glass reactor, under agitation add 90.0mmol diethyl aluminum chloride AlEt
2(MAO, the toluene solution of 1.4mol/L Al/Zr=1400), place reactor-50 ℃ cryostat, and polyreaction is adding 0.5 * 10 for Cl, 90mmol hendecene acyl chlorides and 0.95mL methylaluminoxane
-6Begin behind the mol catalyzer (structure shown in the formula XI as follows).Polymerization adds 10mL hcl acidifying ethanol and stops polyreaction after 12 hours, polymerisate filters the final vacuum drying until constant weight through washing with alcohol.Resulting polymers 2.9g,
1The HNMR test contains hendecene acyl chlorides 30mol%.
Embodiment 16: the multipolymer of p-methylstyrene and polarity alpha-olefin
Under nitrogen protection, to the dry deoxygenation of 250mL, be furnished with the dry p-methylstyrene of adding 1.0mL in the churned mechanically glass reactor, under agitation add 10.0mmol diethyl aluminum chloride AlEt
2(MAO, the toluene solution of 1.4mol/L Al/Zr=1400), place 200 ℃ oil bath with reactor, and polyreaction is adding 0.5 * 10 for Cl, 10mmol ethyl undecylenate and 0.95mL methylaluminoxane
-6Begin behind the mol catalyzer (structure shown in the formula XII as follows).Polymerization adds 10mL hcl acidifying ethanol and stops polyreaction after 5 hours, polymerisate filters the final vacuum drying until constant weight through washing with alcohol.Resulting polymers 2.1g,
1The HNMR test contains ethyl undecylenate 10mol%.
Embodiment 17: the terpolymer of ethene and two kinds of polarity alpha-olefins
Under nitrogen protection, to the dry deoxygenation of 250mL, be furnished with the dry 1-hexenol of adding 1mL in the churned mechanically glass reactor, under agitation add 20.0mmol trimethyl aluminium AlMe
3, (Al/Zr=970), feeding pressure is the ethylene gas of 76mmHg for MAO, the toluene solution of 1.4mol/L, and reactor is placed 125 ℃ oil bath, and polyreaction is adding 1.0 * 10 for 8.0mmol hendecene ammonia and 0.75mL methylaluminoxane
-6Begin behind the mol catalyzer (structure shown in the formula XIII as follows).After the polymerization 10 minutes, add 15mL hcl acidifying ethanol and stop polyreaction, polymerisate filters the final vacuum drying until constant weight through washing with alcohol.Resulting polymers 2.1g,
1The HNMR test contains polar monomer 15mol%.
The multipolymer of embodiment 18:1-butylene and polarity alpha-olefin
Under nitrogen protection, to the dry deoxygenation of 100mL, be furnished with the 1-butylene that adds 10mL in the churned mechanically glass reactor, under agitation add 10.0mmol diethyl aluminum chloride AlEt
2(MAO, the toluene solution of 1.4mol/L Al/Zr=1400), place 0 ℃ ice bath with reactor, and polyreaction is adding 0.5 * 10 for Cl, 10mmol ethyl undecylenate and 1.9mL methylaluminoxane
-6Begin behind the mol catalyzer (seeing structure shown in the following formula (XIII)).Polymerization adds 10mL hcl acidifying ethanol and stops polyreaction after 5 hours, polymerisate filters the final vacuum drying until constant weight through washing with alcohol.Resulting polymers 1.3g,
1The HNMR test contains ethyl undecylenate 56mol%.
Embodiment 19: the multipolymer of propylene and polarity alpha-olefin
Under nitrogen protection, to the dry deoxygenation of 250mL, be furnished with adding 100mL dry toluene in the churned mechanically stainless steel reactor, under agitation add 10.0mmol diethyl aluminum chloride AlEt
2(MAO, the toluene solution of 1.4mol/L Al/Zr=1400), are heated to 200 ℃ with reactor, and polyreaction is adding 0.5 * 10 for Cl, 10mmol ethyl undecylenate and 0.95mL methylaluminoxane
-6Mol catalyzer (seeing structure shown in the following formula (X)) also rises to 100kg/m with propylene pressure
2After begin.Polymerization adds 30mL hcl acidifying ethanol and stops polyreaction after 120 minutes, polymerisate filters the final vacuum drying until constant weight through washing with alcohol.Resulting polymers 4.1g,
1The HNMR test contains ethyl undecylenate 47mol%.
Embodiment 20: the multipolymer of propylene and polarity alpha-olefin
Other uses Ph with embodiment 19
3C
+B (C
6F
5)
4 -Replace MAO, B/Ti mol ratio=1, resulting polymers Semi-polarity alpha-olefin content 45mol%.
Embodiment 21: the terpolymer of ethene, propylene and polarity alpha-olefin
Other is with embodiment 19, with the mixed gas replacement propylene (ethylene/propene pressure ratio=1: 1) of ethylene/propene, gained ter-polymers Semi-polarity alpha-olefin content 36mol%.
Claims (11)
1. alkene/polarity alpha-olefin copolymer is characterized in that:
(a) comprise 30～99.9% moles olefin unit and 0.1～70% mole the polarity alpha-olefin that contains 3-11 carbon atom;
(b) number-average molecular weight that is recorded by gel chromatography is 500-300,000, and range of molecular weight distributions is between 1.0～5.0;
(c) all polymer chains have at least 95% to have at least one unsaturated link(age) in its molecular end;
(d) the B value that is provided by formula (I) is 1.0-2.0:
B＝P
PO/(2P
P·P
O) (I)
In the formula, P
OBe the molfraction of olefin unit in the multipolymer, P
PBe the unitary molfraction of multipolymer Semi-polarity alpha-olefin, P
POBe that polarity alpha-olefin/alkene sequence number accounts for the ratio of all binary sequence numbers;
Described alkene is ethene, propylene, contain the alpha-olefin of 3-10 carbon atom, conjugated diene, non-conjugated diene hydrocarbon;
Described polarity alpha-olefin is the polarity alpha-olefin that contains 3-11 carbon atom, contained one or more polar group is on two keys carbon atom in addition, polar group comprises halogen atom, alkyl, contains the oxygen base, nitrogenous base, contain boryl, contain sulfenyl, phosphorous-containigroups groups, contain silica-based group, and two or more groups can be incorporated into ring in them.
2. alkene as claimed in claim 1/polarity alpha-olefin copolymer is characterized in that, all polymer chains have at least 95% to have at least one unsaturated link(age) in its molecular end in whole molecular weight ranges.
3. alkene as claimed in claim 1/polarity alpha-olefin copolymer is characterized in that, range of molecular weight distributions is between 1.0～3.0.
4. method for preparing the described alkene of claim 1/polarity alpha-olefin copolymer, copolyolefine and contain the polarity alpha-olefin of 3-11 carbon atom and make in the presence of olefin polymerization catalysis, described olefin polymerization catalysis comprises:
(A) transistion metal compound of representing with formula (II),
In the formula: M is the transition metal atoms in the periodic table of elements 3-11 family;
M is the integer of 1-6;
R
1-R
6Can be identical or different; and be respectively hydrogen atom, halogen atom, alkyl, heterogeneous ring compound residue, contain oxygen base, nitrogenous base, contain boryl, contain sulfenyl, phosphorous-containigroups groups, contain silica-based, germanic base, contain tinbase, the silyl that hydrocarbon replaces, siloxy-, alkoxyl group, alkylthio, aryloxy, arylthio, acyl group, ester group, thioester substrate, amido, acylimino, amino, imino-, sulphur ester group, sulfonamido, cyano group or the nitro that hydrocarbon replaces; and two or more groups can be incorporated into ring in them; when m is 2 or when bigger, any two by R
1-R
6The expression group can in conjunction with;
N is a number that satisfies the M valence state;
X is hydrogen atom, halogen atom, alkyl, contain the oxygen base, contain sulfenyl, contain boryl, contain aluminium base, phosphorous-containigroups groups, contain halogen, heterogeneous ring compound residue, contain silica-based, germanic base or contain tinbase, when n is 2 or when bigger, a plurality of X groups can be identical or different, and can be incorporated into ring;
(B) at least aly be selected from following compound:
(B-1) organometallic compound,
(B-2) the Organoaluminoxy hydride compounds and
(B-3) can with the right compound of transistion metal compound (A) reacting forming ion;
Its key step is:
Under the nitrogen atmosphere, with in component A and B-1, B-2 and/or the B-3 adding polymerization reactor, polymerization temperature is-50 ℃ to 200 ℃ with random order, and polymerization pressure is that normal atmosphere is to 100kg/cm
2, polymerization time is 1 minute to 24 hours;
The consumption of component A is 10
-12-10
-2Mol;
The consumption of B component-1 is to make that the mol ratio of the transition metal atoms among B component-1 and the component A is 0.01-100,000;
The consumption of B component-2 is to make that the aluminium atom in the B component-2 and the mol ratio of the transition metal atoms among the component A are 10-500,000;
The consumption of B component-3 is to make that the mol ratio of the transition metal atoms among B component-3 and the component A is 1-10.
5. preparation method as claimed in claim 4 is characterized in that, the consumption of component A is 10
-10-10
-3Mol.
6. preparation method as claimed in claim 4 is characterized in that, the consumption of B component-1 is to make that the mol ratio of the transition metal atoms among B component-1 and the component A is 0.05-50,000.
7. preparation method as claimed in claim 4 is characterized in that, the consumption of B component-2 is to make that the aluminium atom in the B component-2 and the mol ratio of the transition metal atoms among the component A are 20-100,000;
8. preparation method as claimed in claim 4 is characterized in that, the consumption of B component-3 is to make that the mol ratio of the transition metal atoms among B component-3 and the component A is 1.5.
9. preparation method as claimed in claim 4 is characterized in that, polymerization temperature is 0-170 ℃.
10. preparation method as claimed in claim 4 is characterized in that, polymerization pressure is 50kg/cm
2
11. alkene as claimed in claim 1/polarity alpha-olefin copolymer is as the application of superpolymer expanding material.
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| CN 200410088511 CN1769313A (en) | 2004-11-03 | 2004-11-03 | Olefin/polar alpha-olefin copolymer and preparation method and uses |
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| CN104725533A (en) * | 2013-12-18 | 2015-06-24 | 中国石油化工股份有限公司 | Olefin polymerization catalyst, olefin polymerization method, and polyolefin |
| CN105348415A (en) * | 2015-10-22 | 2016-02-24 | 北京理工大学 | Salicylaldehyde amine-based rare earth metal catalyst, preparation method and application |
| US9376459B2 (en) | 2008-11-20 | 2016-06-28 | Japan Polyethylene Corporation | Triarylphosphine or triarylarsine compound, alpha-olefin polymerization catalyst using the compound, ternary copolymer, and production process of alpha-olefin-((meth)acrylic acid)-based copolymer |
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| CN111116804A (en) * | 2018-10-31 | 2020-05-08 | 中国石油化工股份有限公司 | Preparation method of olefin-olefin alcohol copolymer |
| CN114479227A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Polyolefin composition and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9376459B2 (en) | 2008-11-20 | 2016-06-28 | Japan Polyethylene Corporation | Triarylphosphine or triarylarsine compound, alpha-olefin polymerization catalyst using the compound, ternary copolymer, and production process of alpha-olefin-((meth)acrylic acid)-based copolymer |
| US9890231B2 (en) | 2008-11-20 | 2018-02-13 | Japan Polyethylene Corporation | Triarylphosphine or triarylarsine compound, alpha-olefin polymerization catalyst using the compound, ternary copolymer, and production process of alpha-olefin-((meth)acrylic acid)-based copolymer |
| CN104725533A (en) * | 2013-12-18 | 2015-06-24 | 中国石油化工股份有限公司 | Olefin polymerization catalyst, olefin polymerization method, and polyolefin |
| CN104725533B (en) * | 2013-12-18 | 2016-12-07 | 中国石油化工股份有限公司 | A kind of olefin polymerization catalysis and olefine polymerizing process and polyolefin |
| CN105348415A (en) * | 2015-10-22 | 2016-02-24 | 北京理工大学 | Salicylaldehyde amine-based rare earth metal catalyst, preparation method and application |
| CN111116804A (en) * | 2018-10-31 | 2020-05-08 | 中国石油化工股份有限公司 | Preparation method of olefin-olefin alcohol copolymer |
| CN111116804B (en) * | 2018-10-31 | 2022-11-18 | 中国石油化工股份有限公司 | Preparation method of olefin-olefin alcohol copolymer |
| CN110628010A (en) * | 2019-10-18 | 2019-12-31 | 辽宁奥克医药辅料股份有限公司 | Catalyst composition and method for preparing medium molecular weight polyethylene glycol by using same |
| CN114479227A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Polyolefin composition and preparation method and application thereof |
| CN115572341A (en) * | 2022-11-04 | 2023-01-06 | 大连万慷工业科技有限公司 | Functionalized polyolefin elastomer and preparation method thereof |
| CN115572341B (en) * | 2022-11-04 | 2024-04-23 | 大连万慷工业科技有限公司 | Functionalized polyolefin elastomer and preparation method thereof |
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